DE102008014762A1 - Use of polyamine and/or polyammonium-polysiloxane copolymer compound for original equipment of fiber materials including cellulose, wool, cotton, silk and synthetic fibers and as textile softener in finishing of textile fabrics - Google Patents

Abstract

Use of polyamine and/or polyammonium-polysiloxane copolymer compound (I) for original equipment of fiber materials, is claimed. Use of polyamine and/or polyammonium-polysiloxane copolymer compound (I) having units of formula (-[Q-V1a]-) (Ia) for original equipment of fiber materials, is claimed. Q : -NR-, -N +>R 2-, optionally saturated diamino-functional heterocycle of formula (a)-(c), aromatic diamino-functional heterocycle of formula (d), trivalent radical of formula (N) or (N +>(R)) or tetravalent radical of formula (N +>), where Q does not bind to the carbonyl carbon atom; R : H or a monovalent organic radical; V1a : V 1>, V 2>or V 3>; V 2>divalent straight chain, cyclic or branched, optionally saturated or aromatic hydrocarbon radical having up to 1000C (not counting the carbon atoms of the polysiloxane radical Z 2>) and optionally containing one or more groups comprising -O-, -CONH-, -HNCONH-, [1,3]diazetidine-2,4-dion-1,3-yl, CONR 2>-, -C(O)- or -C(S), where V 2>is optionally substituted by one or more hydroxyl groups and/or by -Si(OR) 3 - a(R1a) aand V 2>radical contains at least one -Z 2>- group of formula (-Si(R 1>) 2-O[Si(R 1>) 2-O] n 1-Si(R 1>) 2-); R 2>H or monovalent straight chain, cyclic or branched, optionally saturated or aromatic hydrocarbon radical having up to 100 carbon atoms, containing one or more groups comprising -O-, -NH-, -C(O)- or -C(S)- and optionally substituted by one or more substituents comprising OH, optionally substituted heterocyclic group preferably containing one or more nitrogen atoms, amino, alkylamino, dialkylamino, ammonium, polyether radicals or polyether ester radicals, where, when many -CONR 2>groups are present, they may be the same or different and the R 2>groups in the V 1>and V 2>may be the same or different; a : 0-2; R, R1a : organic radical; R 1>1-22C alkyl, fluoro(1-10C)alkyl, 6-10C aryl or -W 1>-Si(OR) 3 - 1(R1a) a; W 1>-O- or a divalent straight chain, cyclic or branched, optionally saturated or aromatic hydrocarbon having up to 100 carbon atoms, optionally containing one or more groups comprising -C(O)-, -O-, -NH- or -S- groups, and optionally substituted by hydroxyl groups; n1 : 20-1000; V 1>divalent straight chain, cyclic or branched, optionally saturated or aromatic hydrocarbon radicals having up to 1000 carbon atoms and optionally containing one or more groups comprising -O-, -CONH-, -HNCONH-, [1,3]diazetidine-2,4-dion-1,3-yl, CONR 2>-, -C(O)-, -C(S)- or -Z 1>-. where V 1>radical is optionally substituted by one or more hydroxyl groups and/or by -Si(OR) 3 - 1(R1a) a; Z 1>(-Si(R 1>) 2-O[Si(R 1>) 2-O] n 2-Si(R 1>) 2-), where the R 1>groups in V 1>and V 2>groups may be the same or different; n2 : 0-19; V 3>trivalent or higher-valency, straight-chain, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon radical having up to 1000 carbon atoms and optionally containing one or more groups comprising -O-, -CONH-, -HNCONH-, [1,3]diazetidine-2,4-dion-1,3-yl, CONR 2>-, -C(O)-, -C(S)-, -Z 1>, Z 2>or Z 3>, where V 3>is optionally substituted by one or more hydroxyl groups and/or by -Si(OR) 3 - 1(R1a) a; and Z 3>trivalent or higher-valency organopolysiloxane unit. Provided that: (I) contains at least one -Z 1>-, Z 2>or -Z 3>- group; the trivalent and tetravalent Q radicals either serve to branch the main chain formed from Q and V1a such that the valencies which do not serve for binding in the main chain bear further branches formed from -[Q-V1a]- units, or the trivalent and tetravalent Q radicals are saturated by V 3>radicals within a linear main chain without formation of a branch; and the positive charges which result from ammonium groups are neutralized by organic or inorganic acid anions. Independent claims are included for: (1) the use of compositions (II) comprising at least one compound of (I) in combination with at least one other compound having various polydiorganosiloxane units; and (2) an aqueous emulsion comprising at least one compound of (I) or the composition (II), and optionally one or more surfactants and one or more nitrogen-free polysiloxane compounds. [Image].

Description

The This invention relates to the use of polyamino and / or polyammonium-polysiloxane copolymer compounds or aqueous emulsions thereof as original equipment fibrous materials, aqueous emulsions of polyamino and / or polyammonium-polysiloxane copolymer compounds and a method for original equipment of fibrous materials.

Amino-containing polysiloxanes are known as textile plasticizers (US Pat. EP 441 530 ).

It is also known to react α, ω-epoxy-modified siloxanes with α, ω-amino-functionalized alkylene oxides, and to use these products as hydrophilic plasticizers ( US 5,807,956 . US 5,981,681 ). In further development of this idea, block copolymers have been proposed in which α, ω-epoxy-modified siloxanes and α, ω-epoxy-modified polyethers are linked to one another via primary alkylamines as chain extenders. ( US 6,475,568 ). Advantages of these compounds include a higher softness and substrate wetting ability.

Aminosiloxanes with ethylene oxide / propylene oxide units in the side chains have also been described ( US 5,591,880 . US 5,650,529 ).

Increased substantivity is expected from polysiloxane quats ("polysiloxane quats" = quaternary ammonium group-containing polysiloxanes). The reaction of α, ω-diepoxides with tertiary amines in the presence of acids is known, it provides α, ω-diquatäre siloxanes, which can be used for hair care purposes ( DE-A 37 19 086 ). Besides tetraalkyl-substituted quaternary ammonium structures, aromatic imidazolinium derivatives are also claimed.

A reduction in hair washability can be achieved when the α, ω diepoxides are reacted with di-tertiary amines in the presence of acids to form long chain polyquaternary polysiloxanes ( EP-A-282720 ). Aromatic quaternary ammonium structures are not disclosed.

Such polyquaternary imidazolinium derivatives are disclosed in US 6,240,929 treated. These cationic compounds should have a further increased compatibility with the anionic surfactants present in cosmetic formulations. However, hair washout refers to the brief attack of primarily water and very mild, non-irritating skin surfactants, while wash resistant, hydrophilic softeners for textiles have to withstand the attack of concentrated surfactant solutions having high fat and soil release properties. To make matters worse, that modern detergents contain strong alkaline complexing agents, oxidative bleaches and complex enzyme systems and the fibers are often exposed to exposure for hours at elevated temperatures.

By Introduction of alkylene oxide groups in addition to The quaternary ammonium structures should have the hydrophilicity be increased.

Strictly comb-like, ie, alkylene oxide-modified polysiloxane quats in the side groups of the siloxane units have also been described. The hydroxyl groups of comb-like substituted polyethersiloxanes are reacted with epichlorohydrin ( US 5,098,979 ) or chloroacetic acid ( US 5,153,294 . US 5,166,297 ) into the corresponding Chloderivate. This is followed by quaternization with tertiary amines. Disadvantage of the solutions according to US 5,098,979 . US 5,153,294 and US 5,166,297 in that the quat groups are positioned far from the main chain by the alkylene oxide units, thereby weakening the substantivity of the whole molecule.

Branched alkylene oxide-modified polysiloxane quats have been synthesized from α, ω-OH-terminated polysiloxanes and trialkoxysilanes by condensation. The quaternary ammonium structure is introduced via the silane, the quaternary nitrogen atom being substituted by alkylene oxide units ( US 5,602,224 ). Disadvantage of this solution is the less flexible coupling of quat content and degree of branching.

In US 6,242,554 α, ω-difunctional siloxane derivatives are described, each having a separate quaternary ammonium and Alkylenoxideinheit. However, these monoquaternary compounds are not sufficiently substantive.

In the WO 02/10257 and WO 02/10259 polyquaternary polysiloxane block copolymers are claimed as advanced plasticizers that soften textiles during finishing and also alternatively, during the washing process, allow out of detergent formulations. The US-A 2002/0103094 deals with the use of said silicone materials in fabric care formulations. The WO 02/10257 . WO 02/10259 and US-A 2002/0103094 disclose materials in which the quat groups are present partially or fully separated from the alkylene oxide units. These alkylene oxide units are incorporated into the block copolymer as α, ω-difunctional units.

In WO 03/78504 Branched polyquaternary polysiloxane block copolymers are described as permanent fabric softening agents. Inter alia, trifunctional alkylene oxide structures which are separated from the quat groups can be incorporated as branching units. Due to their cross-linked nature, these trifunctional alkylene oxides can be introduced only to a limited extent.

Reactively functionalized branched polyquaternary polysiloxane block copolymers as permanent fabric softening agents are disclosed in US Pat WO 2004/090007 described.

Polyquaternary polysiloxane block copolymers having pendant polyether groups are disclosed in U.S. Pat WO 2006/103075 described as permanent fabric softeners.

Octopus-type polyquaternary polysiloxane block copolymers as permanent fabric softening agents are disclosed in U.S. Pat WO 2007/014930 described.

outgoing from this prior art is a further improvement of the hydrophilicity the silicone-based block copolymers without disclosing the achievable Softness of the treated fibers, especially at constant or improved substantivity (adhesion of the siloxane molecules on the fiber), the flexibility in formulating the Siloxane compositions and the dosage form in particular in the direction on a reduction of the necessary quantities and the material costs very desirable.

It Thus, it is an object of the invention to use polyquaternized Siloxane block copolymers for the original finishing of textiles and other natural and synthetic fibrous Materials such. To provide paper fibers, wool and hair, with which such materials or substrates, preferably textile materials, a silicone-typical softness, improved elasticity and lessened crease tendency with enhanced hydrophilicity becomes.

It It is a further object of the invention to provide a new use of Substances according to the invention as part of Systems for textile original equipment or equipment provide other fibrous substrates.

einem aromatischen diamino-funktionellen Heterocyclus der Formel:

einem dreiwertigen Rest der Formel:

einem dreiwertigen Rest der Formel:

einem vierwertigen Rest der Formel,

worin R jeweils Wasserstoff oder einen einwertigen organischen Rest darstellt,
wobei Q nicht an ein Carbonylkohlenstoffatom bindet,
V aus der Gruppe ausgewählt wird, die aus V¹, V² und V³ besteht, worin
V² ausgewählt wird aus zweiwertigen, geradkettigen, cyclischen oder verzweigten, gesättigten, ungesättigten oder aromatischen Kohlenwasserstoffresten mit bis zu 1000 Kohlenstoffatomen (wobei die Kohlenstoffatome des unten definierten Polysiloxanrestes Z² nicht mitgezählt werden), die gegebenenfalls eine oder mehrere Gruppen, ausgewählt aus
-O-,
-CONH-,

-CONR²-, worin
R² Wasserstoff, einen einwertigen, geradkettigen, cyclischen oder verzweigten, gesättigten, ungesättigten oder aromatischen Kohlenwasserstoffrest mit bis zu 100 Kohlenstoffatomen darstellt, der eine oder mehrere Gruppen ausgewählt aus
-O-,
-NH-,
-C(O)- und
-C(S)- enthalten kann,
und der gegebenenfalls durch eine oder mehrere Substituenten, ausgewählt aus der Gruppe, die besteht aus:
einer Hydroxylgruppe,
einer gegebenenfalls substituierten, bevorzugt ein oder mehrere Stickstoffatome enthaltenden heterocyclischen Gruppe,
Amino,
Alkylamino,
Dialkylamino,
Ammonium,
Polyetherresten und
Polyetheresterresten substituiert sein kann,
wobei, wenn mehrere Gruppen -CONR² vorliegen, diese gleich oder verschieden sein können,
-C(O)- und
-C(S)- enthalten kann, und
der Rest V² gegebenenfalls durch eine oder mehrere Hydroxylgruppen und/oder durch
-Si(OR)_3-a(R')_a
substituiert sein kann, worin a eine ganze Zahl von 0 bis 2 ist und R und R' gleich oder verschieden voneinander sein können und jeweils einen organischen Rest darstellen, und
der Rest V² mindestens eine Gruppe -Z²- der Formel

enthält, worin
R¹ gleich oder verschieden sein kann und aus der Gruppe ausgewählt wird, die besteht aus:
C₁ bis C₂₂-Alkyl,
Fluor(C₁-C₁₀)alkyl, C₆-C₁₀-Aryl und
-W-Si(OR)_3-a(R')_a, worin
R, R' und a wie oben definiert sind, und
W ist
-O- oder
ein zweiwertiger, geradkettiger, cyclischer oder verzweigter, gesättigter, ungesättigter oder aromatischer Kohlenwasserstoffrest mit bis zu 100 Kohlenstoffatomen, der eine oder mehrere Gruppen
-C(O)-,
-O-,
-NH-, und
-S- enthalten kann, und
gegebenenfalls durch Hydroxygruppen substituiert sein kann, und
n₁ = 20 bis 52 bedeutet,
V¹ ausgewählt wird aus zweiwertigen, geradkettigen, cyclischen oder verzweigten, gesättigten, ungesättigten oder aromatischen Kohlenwasserstoffresten mit bis zu 1000 Kohlenstoffatomen, die gegebenenfalls eine oder mehrere Gruppen, ausgewählt aus
-O-,
-CONH-,

-CONR²-, worin
R² wie oben definiert ist, wobei die Gruppen R² in den Gruppen V¹² und V² gleich oder verschieden sein können,
-C(O)-,
-C(S)- und
-Z¹- enthalten können, worin
-Z¹- eine Gruppe der Formel

ist, worin
R¹ wie oben definiert ist, wobei die Gruppen R¹ in den Gruppen V¹² und V² gleich oder verschieden sein können, und
n₂ = 0 bis 19 bedeutet, und
der Rest V¹² gegebenenfalls durch eine oder mehrere Hydroxylgruppen und/oder durch
-Si(OR)_3-a(R')_a
substituiert sein kann, worin a eine ganze Zahl von 0 bis 2 ist und R und R' gleich oder verschieden voneinander sein können und jeweils einen organischen Rest darstellen,
mit der Maßgabe, dass der Rest V¹ keine (Poly)alkylenoxid-Einheiten aufweist,
und
V³ einen drei- oder höherwertigen, geradkettigen, cyclischen oder verzweigten, gesättigten, ungesättigten oder aromatischen Kohlenwasserstoffrest mit bis zu 1000 Kohlenstoffatomen darstellt, der gegebenenfalls eine oder mehrere Gruppen, ausgewählt aus
-O-,
-CONH-,

-CONR²-, worin R² wie oben definiert ist,
-C(O)-,
-C(S)-,
-Z¹-, das wie oben definiert ist,
-Z²- das wie oben definiert ist, und
Z³, worin Z³ eine drei- oder höherwertige Polyorganosiloxaneinheit ist,
enthalten kann, und
der gegebenenfalls durch eine oder mehrere Hydroxylgruppen und/oder durch
-Si(OR)_3-a(R')_a
substituiert sein kann, worin a eine ganze Zahl von 0 bis 2 ist und R und R' gleich oder verschieden voneinander sein können und jeweils einen organischen Rest darstellen,
mit der Maßgabe,

• – dass die genannte Polyamino- und/oder Polyammonium-Polysiloxan-Copolymer-Verbindungen mindestens eine Gruppe -Z¹-, -Z²- oder Z³ enthalten, und
• – dass die drei- und vierwertigen Reste Q entweder der Verzweigung der aus Q und V gebildeten Hauptkette dienen, so dass die Valenzen, die nicht der Bindung in der Hauptkette dienen, weitere aus -[Q-V]-Einheiten gebildete Verzweigungen tragen, oder die drei- und vierwertigen Reste Q sättigen sich mit Resten V³ innerhalb einer linearen Hauptkette ohne Bildung einer Verzweigung ab, und

und worin die aus Ammoniumgruppen resultierenden positiven Ladungen durch organische oder anorganische Säureanionen neutralisiert sind,
zur Erstausrüstung von Fasermaterialien.It has surprisingly been found that the objects described above can be achieved by the use of polyamino and / or polyammonium-polysiloxane copolymer compounds which have repeating units of the formula (I): - [QV] - (I) wherein Q is selected from the group consisting of:
-NO-,
-N ⁺ R ₂ -
a saturated or unsaturated diamino-functional heterocycle of the formulas:

an aromatic diamino-functional heterocycle of the formula:

a trivalent radical of the formula:

a trivalent radical of the formula:

a tetravalent radical of the formula

wherein each R is hydrogen or a monovalent organic radical,
where Q does not bind to a carbonyl carbon atom,
V is selected from the group consisting of V ¹ , V ² and V ³ , wherein
V ^{2 is} selected from divalent, straight-chain, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon radicals having up to 1000 carbon atoms (excluding the carbon atoms of the polysiloxane radical Z ² defined below), optionally one or more groups selected from
-O-,
-CONH-,

-CONR ² - in which
R ^{2 represents} hydrogen, a monovalent, straight-chain, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon radical having up to 100 carbon atoms and having one or more groups selected from
-O-,
-NH-,
-C (O) - and
-C (S) - may contain
and optionally substituted by one or more substituents selected from the group consisting of:
a hydroxyl group,
an optionally substituted, preferably one or more nitrogen atoms-containing heterocyclic group,
amino,
alkylamino,
dialkylamino,
Ammonium,
Polyether radicals and
Polyetheresterresten may be substituted,
where, if there are several groups -CONR ² , these may be the same or different,
-C (O) - and
-C (S) - may contain, and
the radical V ² optionally by one or more hydroxyl groups and / or by
-Si (OR) _3-a (R ') _a
wherein a is an integer of 0 to 2 and R and R 'may be the same or different and each represents an organic group, and
the radical V ^{2 is} at least one group -Z ² - of the formula

contains, in which
R ^{1 may be the} same or different and is selected from the group consisting of:
C ₁ to C ₂₂ alkyl,
Fluoro (C ₁ -C ₁₀ ) alkyl, C ₆ -C ₁₀ aryl and
-W-Si (OR) _3-a (R ') _a , wherein
R, R 'and a are as defined above, and
W is
-O- or
a divalent, straight-chain, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon radical having up to 100 carbon atoms and having one or more groups
-C (O) -,
-O-,
-NH-, and
-S- may contain, and
optionally substituted by hydroxy groups, and
n ₁ = 20 to 52,
V ^{1 is} selected from divalent, straight-chain, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon radicals having up to 1000 carbon atoms, optionally one or more groups selected from
-O-,
-CONH-,

-CONR ² - in which
R ^{2 is} as defined above, where the groups R ² in the groups V ¹² and V ^{2 may be} identical or different,
-C (O) -,
-C (S) - and
-Z ¹ -, wherein
-Z ¹ - a group of the formula

is in which
R ^{1 is} as defined above, wherein the groups R ¹ in the groups V ¹² and V ^{2 may be the} same or different, and
n ₂ = 0 to 19, and
the radical V ¹² optionally by one or more hydroxyl groups and / or by
-Si (OR) _3-a (R ') _a
where a is an integer from 0 to 2 and R and R 'may be the same or different and each represents an organic radical,
with the proviso that the radical V ^{1 has} no (poly) alkylene oxide units,
and
V ^{3 is} a trivalent or higher, straight-chain, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon radical having up to 1000 carbon atoms, optionally one or more groups selected from
-O-,
-CONH-,

-CONR ² -, wherein R ^{2 is} as defined above,
-C (O) -,
-C (S) -,
-Z ¹ - which is as defined above
-Z ² - which is as defined above, and
Z ³ , wherein Z ^{3 is} a tri- or higher polyorganosiloxane unit,
can contain, and
optionally substituted by one or more hydroxyl groups and / or by
-Si (OR) _3-a (R ') _a
where a is an integer from 0 to 2 and R and R 'may be the same or different and each represents an organic radical,
with the proviso

• - That said polyamino and / or polyammonium-polysiloxane copolymer compounds contain at least one group -Z ¹ -, -Z ² - or Z ³ , and
• - That the trivalent and tetravalent radicals Q serve either the branching of the main chain formed from Q and V, so that the valencies, which do not serve the bond in the main chain, carry further branches formed from - [QV] units, or the three and tetravalent radicals Q are saturated with residues V ³ within a linear main chain without formation of a branch, and

and wherein the positive charge resulting from ammonium groups is neutralized by organic or inorganic acid anions,
for the original equipment of fiber materials.

In a preferred embodiment of the invention, the polysiloxane compound of the formula (I) contains V ² and V ¹ units.

The group R in the definition of Q is preferably selected from the groups R ² .

eine quaternierte Imidazoleinheit der Struktur

eine quaternierte Pyrazoleinheit der Struktur

Preferred embodiments of Q are:
For radicals of the formula

a quaternized imidazole moiety of the structure

a quaternized pyrazole unit of the structure

eine zweifach quaternierte Piperazineinheit der Struktur

For radicals of the formula

a doubly quaternized piperazine moiety of structure

eine monoquaternierte Piperazineinheit der Struktur

eine monoquaternierte Piperazineinheit der StrukturFor radicals of the formula

a monoquaternized piperazine moiety of the structure

a monoquaternized piperazine moiety of the structure

eine monoquaternierte Einheit der Struktur

eine zweifach quaternierte Einheit der Struktur

und eine monoquaternierte Einheit der Struktur

For radicals of the formula -N ⁺ R ₂ - a radical of the formula -N ⁺ R ² -, wherein R represents a monovalent, straight-chain, cyclic or branched, saturated hydrocarbon radical having up to 20 carbon atoms, the one or more groups selected from
-O-,
-NH-,
-C (O) - and
-C (S) - may contain
and which may optionally be substituted by one or more hydroxyl groups, and
a doubly quaternized unit of structure

a monoquaternized unit of the structure

a doubly quaternized unit of structure

and a monoquaternized unit of the structure

eine monoquaternierte Einheit der Struktur

worin:
t von 2 bis 10 ist,
R wie oben definiert, bevorzugt R² ist, R² wie oben definiert ist, und die Bedeutung von R² von der Bedeutung der obigen Gruppe R² gleich oder verschieden sein kann,
R³ die Bedeutung von R² aufweist, wobei R² und R³ gleich oder verschieden sein können, oder
R² und R³ gemeinsam mit dem positiv geladenen Stickstoffatom einen fünf- bis siebengliedrigen Heterocyclus bilden können, der gegebenenfalls zusätzlich ein oder mehrere Stickstoff-, Sauerstoff- und/oder Schwefelatome aufweisen kann,
R⁵, R⁶, R⁷ gleich oder verschieden sein können und aus der Gruppe ausgewählt werden, die besteht aus: H, Halogen, Hydroxylgruppe, Nitrogruppe, Cyanogruppe, Thiolgruppe, Carboxylgruppe, Alkylgruppe, Monohydroxyalkylgruppe, Polyhydroxyalkylgruppe, Thioalkylgruppe, Cyanoalkylgruppe, Alkoxygruppe, Acylgruppe, Acetyloxygruppe, Cycloalkylgruppe, Arylgruppe, Alkylarylgruppe, und Gruppen des Typs -NHR^W, in denen R^W H, Alkylgruppe, Monohydroxyalkylgruppe, Polyhydroxyalkylgruppe, Acetylgruppe oder eine Ureidogruppe bedeuten, und jeweils zwei der benachbarten Reste R⁵, R⁶ und R⁷ mit den sie an den Heterocyclus bindenden Kohlenstoffatomen aromatische Fünf- bis Siebenringe bilden können, und
R⁸ die Bedeutung von R² aufweist, wobei R⁸ und R² gleich oder verschieden sein können.For radicals of the formula -NO a monoquaternized unit of the structure

a monoquaternized unit of the structure

wherein:
t is from 2 to 10,
R as defined above, preferably R ^2, R ² is as defined above, and the meaning of R ² from the meaning of the above group R ² can be identical or different,
R ^{3 has} the meaning of R ² , wherein R ² and R ^{3 may be the} same or different, or
R ² and R ³ together with the positively charged nitrogen atom can form a five- to seven-membered heterocycle which may optionally additionally have one or more nitrogen, oxygen and / or sulfur atoms,
R ⁵ , R ⁶ , R ^{7 may be the} same or different and are selected from the group consisting of: H, halogen, hydroxyl, nitro, cyano, thiol, carboxyl, alkyl, monohydroxyalkyl, polyhydroxyalkyl, thioalkyl, cyanoalkyl, alkoxy, Acyl group, acetyloxy group, cycloalkyl group, aryl group, alkylaryl group, and groups of the type -NHR ^W , in which R ^{W is} H, alkyl group, monohydroxyalkyl group, polyhydroxyalkyl group, acetyl group or a ureido group, and in each case two of the adjacent radicals R ⁵ , R ⁶ and R ⁷ with which they can form aromatic five- to seven-membered rings on the heterocycle-bonding carbon atoms, and
R ^{8 has} the meaning of R ² , wherein R ⁸ and R ^{2 may be the} same or different.

oder eine vierwertigen Rest

darstellt, dienen diese Reste bei den linearen Copolymeren der Formel (I) bevorzugt nicht der Verzweigung der Polysiloxan-Copolymere sondern diese Reste sind ausschließlich mit insbesondere dreiwertigen Resten V³ verbunden, wobei cyclische Strukturen ausgebildet werden, die Bestandteil der linearen Hauptkette sind, wie z. B. ein Strukturelement der Formel:

In the case that Q is a trivalent residue of the formulas

or a quadrivalent residue

represent these radicals in the linear copolymers of the formula (I) is preferably not the branching of the polysiloxane copolymers but these radicals are exclusively connected to trivalent particular V ³ , wherein cyclic structures are formed which are part of the linear main chain, such as , B. a structural element of the formula:

worin Q, V¹ und V² wie zuvor definiert sind, und das Verhältnis von w zu v ungefähr 1:1 beträgt.In a preferred embodiment of the invention, the polyamino and / or polyammonium-polysiloxane copolymer compounds have the formula (II):

wherein Q, V ¹ and V ^{2 are} as previously defined, and the ratio of w to v is about 1: 1.

The used in the invention polyamine and / or Polyammonium-polysiloxane copolymer compounds generally have on average at least two, more preferably at least three repeat units of the formula (I).

According to the invention However, it is also possible on a case by case basis to have only one repeat unit of the formula (I) is present. In this case, there are so-called "butterfly" structures Q-V-Q or V-Q-V. The formation of these compounds is by Adjustment of the molar ratio of the starting materials allows.

In a preferred embodiment of the polysiloxane compounds of the formula (I), V ^{2 represents} a group of the formula -V ² * -Z ² -V ² * - in which Z ^{2 is} as defined above and V ² * represents a divalent straight-chain, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon radical having up to 40 carbon atoms which may optionally have one or more groups selected from -O-, -CONH- , -CONR ² -, wherein R ^{2 is} as defined above, -C (O) - and -C (S) - may contain, and the radical V ² * may optionally be substituted by one or more hydroxyl groups.

In the above-mentioned embodiment, the preferably linear polysiloxane copolymer used in the present invention may have the following repeating units:
- [V ² * -Z ² -V ² * -Q] - preferably together with - [V ¹ -Q] -.

-CONR²-, worin R² wie oben definiert ist, , -C(O)-, -C(S)- und -Z¹- enthalten kann, worin -Z¹- eine Gruppe der Formel

ist, worin
R¹ C₁-C₁₈-Alkyl, das gegebenenfalls mit einem oder mehreren Fluoratomen substituiert sein kann, oder Phenyl ist, und n₂ wie oben definiert ist.In a preferred embodiment of the polysiloxane compound of the formula (I) used according to the invention, the group V ^{1 is} selected from divalent, straight-chain, cyclic or branched, ge saturated, unsaturated or aromatic hydrocarbon radicals having up to 600, preferably up to 400 carbon atoms, which may optionally have one or more groups selected from -O-, -CONH-,

-CONR ² -, wherein R ^{2 is} as defined above, -C (O) -, -C (S) - and -Z ¹ - may contain, wherein -Z ¹ - a group of the formula

is in which
R ^{1 is} C ₁ -C ₁₈ alkyl, which may be optionally substituted with one or more fluorine atoms, or phenyl, and n _{2 is} as defined above.

worin R² wie oben definiert ist, bevorzugt H oder Alkyl, bevorzugt mit 1 bis 6 Kohlenstoffatomen, ist und R³ die Bedeutung von R² besitzt und bevorzugt H, Alkyl, bevorzugt mit 1 bis 6 Kohlenstoffatomen, oder R^O ist, worin der Rest R^O eine Gruppe der Formel (IV) darstellt: -X-E-Y (IV),worin X eine Einfachbindung oder einen zweiwertigen, geradkettigen, verzweigten oder cyclischen Kohlenwasserstoffrest mit bis zu 20 Kohlenstoffatomen darstellt, der gegebenenfalls Stickstoff und/oder Sauerstoff enthalten kann, und X über ein Kohlenstoffatom mit dem Stickstoffatom von Q verbunden ist,
E einen Polyalkylenoxidrest der Formel -[(C_aH_2a)O]_y worin a = 2 bis 4 ist, und
y = 2 bis 10000, bevorzugt 2 bis 40 ist,
der über ein Kohlenstoffatom mit der Gruppe X und über ein Sauerstoffatom mit der Gruppe Y verbunden ist,
Y Wasserstoff oder einen einwertigen, geradkettigen, verzweigten oder cyclischen, gesättigten, ungesättigen oder aromatischen Kohlenwasserstoffrest mit bis zu 24 Kohlenstoffatomen darstellt, der Sauerstoff und/oder Stickstoff und/oder Halogen enthalten kann und über ein Kohlenstoffatom mit der Gruppe E verbunden ist.In a further preferred embodiment of the polysiloxane compounds of the formula (I), the group Q is selected from:

wherein R ^{2 is} as defined above, preferably H or alkyl, preferably having 1 to 6 carbon atoms, and R ^{3 has} the meaning of R ² and is preferably H, alkyl, preferably having 1 to 6 carbon atoms, or R ^O , wherein the Rest R ^{O represents} a group of the formula (IV): -XEY (IV), wherein X represents a single bond or a divalent, straight-chain, branched or cyclic hydrocarbon radical having up to 20 carbon atoms, which may optionally contain nitrogen and / or oxygen, and X is connected via a carbon atom to the nitrogen atom of Q,
E is a polyalkylene oxide radical of the formula - [(C _a H _2a ) O] _y wherein a = 2 to 4, and
y = 2 to 10,000, preferably 2 to 40,
which is connected via a carbon atom to the group X and via an oxygen atom to the group Y,
Y represents hydrogen or a monovalent, straight-chain, branched or cyclic, saturated, unsaturated or aromatic hydrocarbon radical having up to 24 carbon atoms, which may contain oxygen and / or nitrogen and / or halogen and is connected via a carbon atom with the group E.

wobei es sich um statistische und blockartige Sequenzen der Ethylen- und Propylenoxid-Einheiten handeln kann und die Bindung an E über eine Ethylen- oder Propylenoxid-Einheit erfolgen kann, die Darstellung der Gruppe (V) mithin nur quantitativ ist,
mit
v = 1 bis 200, bevorzugt 1 bis 40
w = 0 bis 200, bevorzugt 0 bis 10
v + w ≥ 1.Preferably, R ^{0 is} a group of the formula (III) in which -E- represents a group of the formula (V):

which may be random and block-like sequences of the ethylene and propylene oxide units and the bond to E can take place via an ethylene or propylene oxide unit, the representation of the group (V) is therefore only quantitative,
With
v = 1 to 200, preferably 1 to 40
w = 0 to 200, preferably 0 to 10
v + w ≥ 1.

In the group of the formula (IV), furthermore, Y is preferably selected from H or straight-chain, cyclic, branched C ₁ to C ₂₂ -alkyl, alkenyl, alkynyl, fluoro (C ₁ -C ₁₀ ) -alkyl and C ₆ -C ₁₀ aryl radicals selected.

für -NH₂ ⁺-, -N(CH₃)₂ ⁺-, -(NHR^O)⁺-.Particularly preferred is

for -NH ₂ ⁺ -, -N (CH ₃ ) ₂ ⁺ -, - (NHR ^O ) ⁺ -.

V ² * is preferably a bivalent straight, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon radical having up to 16 carbon atoms and having one or more groups selected from -O-, -CONH-, -CONR ² -, wherein R ² as defined above, -C (O) -, -C (S) - and may be substituted with one or more hydroxyl groups. Even more preferably, -V ² * - is selected from groups of the formulas:

The term (poly) alkylene oxide-free means that the radical V ^{1 contains} no alkylene ether group or poly (alkylene ether) group.

ist, worin
R¹ wie oben definiert ist, wobei die Gruppen R¹ in den Gruppen V¹ und V² gleich oder verschieden sein können, und
n₂ = 0 bis 19 bedeutet, und
der Rest V¹ gegebenenfalls durch eine oder mehrere Hydroxylgruppen und/oder durch
-Si(OR)_3-a(R')_a
substituiert sein kann, worin a eine ganze Zahl von 0 bis 2 ist und R und R' gleich oder verschieden voneinander sein können und jeweils einen organischen Rest darstellen.V ¹ is preferably selected from divalent, straight-chain, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon radicals having up to 100 carbon atoms, optionally one or more groups selected from
-Z ¹ -, wherein
-Z ¹ - a group of the formula

is in which
R ^{1 is} as defined above, wherein the groups R ¹ in the groups V ¹ and V ^{2 may be the} same or different, and
n ₂ = 0 to 19, and
the radical V ¹ optionally by one or more hydroxyl groups and / or by
-Si (OR) _3-a (R ') _a
wherein a is an integer of 0 to 2 and R and R 'may be the same or different from each other and each represents an organic residue.

• – -R⁹-, worin R⁹ einen zweiwertigen, gesättigten oder einfach oder mehrfach ungesättigten, geradkettigen oder verzweigten Kohlenwasserstoffrest mit zwei bis 25 Kohlenstoffatomen darstellt,

V¹ ist bevorzugt:
-[CH₂]_o
mit o = 2 bis 8, bevorzugter o = 2 bis 6, am meisten bevorzugt = 6.V ¹ is more preferably for

• --R ⁹ -, in which R ^{9 represents} a divalent, saturated or mono- or polyunsaturated, straight-chain or branched hydrocarbon radical having from 2 to 25 carbon atoms,

V ¹ is preferred:
- [CH ₂ ] _o
with o = 2 to 8, more preferably o = 2 to 6, most preferably = 6.

V²* = zweiwertiger gesättigter Kohlenwasserstoffrest mit 1 bis 10 Kohlenstoffatomen darstellt, und
-Z²- einen Rest der Formel

darstellt, worin
R¹ C₁ bis C₂₂-Alkyl, bevorzugt Methyl ist, und
n₁ = 22 bis 50, noch bevorzugter 24 bis 48 bedeutet.Polyamino and / or polyammonium-polysiloxane copolymer compounds of the formula (I) are particularly preferably used according to the invention:
wherein at least one, preferably at least two, more preferably all of the following features are fulfilled:
V ¹ is a group of the formula - [CH ₂ ] _o -, where o = 2 to 6, more preferably o = 6,
V ² is a group V ² * -Z ² -V ² * - with V ² * =

V ² * = divalent saturated hydrocarbon radical having 1 to 10 carbon atoms, and
-Z ² - a radical of the formula

represents, in which
R ^{1 is} C ₁ to C ₂₂ alkyl, preferably methyl, and
n ₁ = 22 to 50, more preferably 24 to 48.

In particular, the polyamino and / or polyammonium-polysiloxane copolymer compounds of the invention can be prepared by a process in which diamines are reacted with amino-reactive compounds, such as epoxy and / or haloalkyl-functional compounds, the reacted compounds having at least one Containing polydiorganosiloxane radical and at least one radical which leads to the formation of a radical V ¹ .

at the polysiloxane copolymer compounds of the invention these may be those which have amino functions and they may be those which have ammonium functions. Preferably, the inventive Polysiloxane copolymer compounds to polyammonium-polysiloxane copolymer compounds. These are preferably by quaternizing reaction di-tertiary Diamines with quaternizing or alkylating compounds, such as in particular epoxy and / or haloalkyl-functional compounds receive.

Examples of neutralizing anions resulting from the ammonium groups are: halide ions, especially chloride and bromide, alkyl sulfates, especially methosulfate, carboxylates, especially acetate, propionate, octanoate, decanoate, dodecanoate, tetradecanoate, hexadecanoate, octadecanoate, oleate, sulfonates, especially toluenesulfonate. As a non-neutralizing anion for the quater nated compounds is also the OH ^- anion into consideration. Through internal exchange, other anions can be introduced. These include, for example, organic anions, such as polyether carboxylates and polyether sulfates.

• a) Ein Diamin, welches keine (Poly)alkylenoxidgruppe enthält, mit aminoreaktiven Polysiloxan-enthaltenden Verbindungen umgesetzt wird, und
• b) Ein Diamin, welches ein Polysiloxan enthält, mit amino-reaktiven Verbindungen umgesetzt wird, die kein (Poly)alkylenoxid enthalten.

The polyammonium-polysiloxane copolymer compounds according to the invention are preferably those which are prepared, for example, by a process in which

• a) a diamine containing no (poly) alkylene oxide group is reacted with amino-reactive polysiloxane-containing compounds, and
• b) a diamine containing a polysiloxane is reacted with amino-reactive compounds containing no (poly) alkylene oxide.

By suitable selection of the stoichiometry of the starting compounds, the ratio of the groups V ¹ and V ² in the compounds according to the invention can be controlled.

Suitable V ¹ introducing monomers are, for example, alpha, omega-diamines, such as alkylenediamines. These are reacted with, for example, amino-reactive V ² -containing monomers, such as, for example, diepoxy-polysiloxane compounds, dihaloalkyl-polysiloxane compounds.

Alternatively, V ^{1 can} also be introduced via dihaloalkyl compounds, diepoxide compounds or mixed-group compounds reacted with amino-functional monomers which introduce group V ² or further groups V ¹ .

For the preparation of the polyamino and / or polyammonium-polysiloxane copolymer compounds used according to the invention, it is possible, for example, to refer to the WO 02/10257 to get expelled.

worin a, b und c gleich oder verschieden und von 1 bis 40 sein können,

mit q + r ≥ 0, wobei die Anordnung der Ethylen- und Propylenoxid-Einheiten statistisch oder blockartig sein kann und die Anbindung an Q über Ethylen- und Propylenoxid-Einheiten via ein Kohlenstoffatom erfolgen kann.The polysiloxanes of the general formula (I) according to the invention may optionally also contain branching units V ³ . It is useful to V ^{3 is} a trivalent or higher, straight-chain, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon radical having up to 1000 carbon atoms, optionally one or more groups selected from -O-, -CONH-, -CONR ² -, wherein R ^{2 is} as defined above, -C (O) -, -C (S) -, -Z ¹ -, which is as defined above, -Z ² - which is as defined above, and Z is ³ , wherein Z ^{3 is} a tri- or higher polyorganosiloxane unit may contain. The branching unit V ³ may be silicone-free. Examples of these include:

wherein a, b and c may be the same or different and from 1 to 40,

with q + r ≥ 0, where the arrangement of the ethylene and propylene oxide units may be random or block-like and the attachment to Q via ethylene and propylene oxide units via a carbon atom can take place.

worin R¹ wie oben definiert ist, m = 0 bis 1000, bevorzugt 0 bis 50 und m¹ ≥ 1 und m² ≥ 3 ist,

worin R¹ jeweils wie oben definiert ist.The branching unit V ³ may contain a tri- or higher polyorganosiloxane unit, such as:

wherein R ^{1 is} as defined above, m = 0 to 1000, preferably 0 to 50 and m ¹ ≥ 1 and m ² ≥ 3,

wherein R ^{1 is in} each case as defined above.

An example of a Z ³ -containing branching unit V ³ is, for example:

The polysiloxanes according to the invention may contain units R ⁰ which are preferably incorporated into the polymer by suitable alkylation reactions of primary, secondary or tertiary monoamino-functionalized polyalkylene oxides with reactively functionalized siloxane precursors. The primary mono functionalized Jeffamine ^® M series (Huntsman Corp.) are preferably used.

Monofunctionally bonded hydrophilic elements R ^O can be introduced into the polysiloxane copolymers according to the invention in order to increase the hydrophilicity in a targeted manner.

This leads both to an increased hydrophilicity of the invention Polysiloxane copolymers themselves, so that, for example, more stable emulsions arise in water, as well as to increase the hydrophilicity with the polysiloxane copolymers according to the invention treated substrates, for example, an improved Moisture absorption leads.

-Si(OR)_3-a(R')_a worin 'a' eine ganze Zahl von 0 bis 2 ist und R und R' gleich oder verschieden voneinander sein können und jeweils einen organischen Rest darstellen. Die genannten reaktiven Gruppen können erfindungsgemäß über V oder Q entsprechenden Einheiten eingeführt werden, wie in der PCT/EP 2004/050472 näher beschrieben.It is further within the scope of the invention to introduce reactive units into the copolymer backbone. Such reactive groups include groups of the following formulas:

-Si (OR) _3-a (R ') _a wherein 'a' is an integer from 0 to 2 and R and R 'may be the same or different and each represents an organic radical. The reactive groups mentioned can be introduced according to the invention via units corresponding to V or Q, as in US Pat PCT / EP 2004/050472 described in more detail.

The polyamine and / or polyammonium-polysiloxane copolymer compounds of the present invention may be solid or liquid at 25 ° C. In the event that they are liquid at 25 ° C, the viscosities of said polysiloxanes are preferably between 500 to 50,000,000 mPa · s at 25 ° C, preferably 1000 to 2,500,000 mPa · s at 25 ° C and a Shear rate gradient of D = 1 s ^-1 .

The invention further relates to aqueous emulsions containing at least one polyamino and / or polyammonium-polysiloxane copolymer compounds and their use for the initial finishing of fiber materials. Such aqueous emulsions are prepared by dispersing the polyamino and / or polyammonium-polysiloxane copolymer compounds or optionally alcoholic solutions in water with conventional emulsifying apparatus, such as rotor-stator mixers, simple stirrers and mixing nozzles and Gaulin emulsifying, optionally in the presence of a or more surfactants. Preferably, concentrates are first prepared, which are then diluted to the preferred use concentrations. Concentration ranges of the concentrates are for example: component concentrations Polyamino and / or polyammonium polysiloxane copolymer compounds 10 to 40% by weight emulsifiers 0.5 to 20% by weight Water and optionally organic solvents rest

Concentration ranges of the application emulsions are for example: component concentrations Polyamino and / or polyammonium polysiloxane copolymer compounds 1 to 10% by weight emulsifiers 0.05 to 5% by weight Water and optionally organic solvents rest

Applicable surfactants include:
Preference is given to silicone-free, preferably cationic or nonionic surfactants.

The Application of anionic surfactants is possible in principle, but less preferred. In the preferred cationic surfactants is at least one constituent consisting of unpolymerized, organic, quaternary ammonium compounds is selected. Preference is given to quaternary groups containing hydrocarbon groups Ammonium salts or amine salts, wherein the hydrocarbon groups preferably contain from 8 to 28 carbon atoms. Examples nonionic surfactants include alkoxylated alcohols, Ethylene oxide (EO) propylene oxide (PO) block polymers, polyhydroxy fatty acid amides, Alkyl polysaccharides and the like.

The non-aqueous vehicles, which may be present in the emulsions in addition to water, are, for example, organic solvents, preferably water-soluble organic solvents alone and / or mixtures thereof also with water. Preferred organic solvents include monoalcohols, diols, polyols such as glycerine, glycol, polyethers such as polyalkylene glycols such as polyethylene glycols and mixtures thereof, also with water. Particular preference is given to mixtures of solvents, in particular mixtures of lower aliphatic alcohols, such as ethanol, propanol, butanol, isopropanol, and / or diols, such as 1,2-propanediol or 1,3-propanediol; or mixtures thereof with glycerin. Suitable alcohols include in particular C ₁ -C ₄ -alcohols. Preference is given to 1,2-propanediol and water.

The aqueous emulsion formulations may also even more aids in the usual for these tools Contain quantities. Usual aids in the context of the invention are u. a. Leveling agent, wetting agent, gloss finish, Fiber preservatives, slip resistance and other aids after State of the art. A good overview of the invention Auxiliaries can be found in Chwala / Anger, Handbuch der Textilhilfsmittel, Verlag Chemie, Weinhein 1977. In addition, can Buffer systems for setting an optimum pH value during the equipment are incorporated.

The The invention further relates to the use of compositions containing at least one polyamino and / or polyammonium-polysiloxane copolymer compounds with at least one other polydiorganosiloxane compound different therefrom. As of the polyamino and / or polyammonium-polysiloxane copolymer compounds various polydiorganosiloxane compounds come in particular those compounds which do not have amino and ammonium functions wear, like PDMS oils.

The invention further relates to a method of finishing fiber materials which comprises treating the fiber materials with at least one polyamino and / or polyammonium-polysiloxane copolymer compound as defined above or a composition as defined above, or an aqueous emulsion thereof. The finishing process can be carried out in particular by the continuous process (padding or lisseuse process) or by the exhaustion process (jet process). Examples of technological parameters to be adhered to in these finishing processes include: • Continues (eg, Foulard, Lisseuse) Equipment Temperature: room temperature Drying temperature: 75-105 ° C in a convection oven or 10-60 sec on a tenter at 150 ° C, especially 30-45 sec Time in convection oven: 10-20 minutes • extraction process (eg jet, reel skid) Equipment Temperature: 30-60 ° C, preferably 35-50 ° C and especially 35-45 ° C. heating rate: 2-4 ° C / minute Equipment time: 15-25 minutes Liquor ratio: 1: 5 to 1:50, especially 1:10 to 1:30 drying temperature 75-105 ° C in a convection oven or 10-60 sec on a tenter at 150 ° C, especially 30-45 sec Time in convection oven: 10-20 minutes

The Polyamine and / or used according to the invention used Polyammonium-polysiloxane copolymer compounds or their compositions or their aqueous emulsions are outstandingly suitable as fabric softener in the finishing of textile fabrics, especially those of cotton or blends of cotton with polyester, polyamide, polyacrylonitrile, wool and silk. Under textile Fabrics are preferably woven, knitted or knitted fabric and to understand fleeces. As particularly advantageous has the Use for the equipment of cotton or cotton textiles containing anionic whiteners pretreated, proved by the jet process.

The The invention further relates to the use of the invention Compounds for the original equipment and treatment of textiles and other natural and synthetic fibrous Materials, including paper, hair and wool.

The Invention and the effects achieved with it are by the following Examples illustrated.

EXAMPLES

Example 1 (according to the invention)

gemischt und anschließend für 9,5 Stunden auf Rückflußtemperatur erhitzt. Es wird eine gelbe trübe Lösung erhalten.In a 250 ml three-necked flask at room temperature, 6.94 g of water, 3.47 g of 2-propanol, 2.7 g (31.36 mmol amino groups) of N, N, N ', N'-tetramethyl-1,6-hexanediamine , 6.28 g (31.36 mmol) of dodecanoic acid and 50 g (31.36 mmol of epoxy groups) of an epoxysiloxane of the average composition

mixed and then heated to reflux for 9.5 hours. A yellow cloudy solution is obtained.

The epoxide conversion is quantitative ( ¹ H NMR).

The Solution has a polymer content of 85%.

The polymer contains structural units of the formula

Example 2 (not according to the invention)

gemischt und anschließend zur Reaktion gebracht werden.The procedure described in Example 1 is repeated with the difference that 6.64 g of water, 3.32 g of 2-propanol, 1.94 g (22.52 mmol of amino groups) of N, N, N ', N'-tetramethyl 1,6-hexanediamine, 4.51 g (22.52 mmol) dodecanoic acid and 50 g (22.52 mmol epoxy groups) of an epoxysiloxane of average composition

mixed and then reacted.

It a yellow cloudy solution is obtained.

The epoxide conversion is quantitative ( ¹ H NMR).

The Solution has a polymer content of 85%.

The polymer contains structural units of the formula

Example 3

Production of microemulsions, textile equipment, washing tests

The polymers according to Examples 1 and 2 are converted into 2% microemulsions of the following composition:
0.7 g of polymer solution according to Examples 1 and 2 (each 85% active content)
0.128 emulsifier imbentin T 060
0.272 emulsifier imbentin T 120
28.9 g of water

Subsequently will cotton terry at 40 ° C for 30 minutes equipped with the microemulsions in the extraction process. The amount of polymer used is 10 mg polymer / 1 g cotton terry. Then the finished terry cloth rags dried at 80 ° C for 30 minutes and in two Parts shared.

from first part of the terrycloths becomes after 72 storage the first grip and determines the hydrophilicity.

Of the second part of the terrycloth will be 3 wash cycles in the presence of a subjected to anionic surfactants based reference detergent (40 ° C, 30 minutes, 0.1 g / l wfk Ecolabel Reference Detergent Light Duty (wfk Institute for Applied Research GmbH Fichtenhain 11 D-47807 Krefeld), after each wash for 5 minutes with tap water rinse) and then stored for 24 hours. Also from the terrycloths after 3 washing cycles we handle and determines the hydrophilicity.

• *Es werden die Ergebnisse von 5 Versuchslappen, bewertet von 4 Personen, gemittelt.
• **Auf einen ausgerüsteten Frotteelappen werden 10 Wassertropfen (50 μl) aufgesetzt, die Zeiten in Sekunden bis zum Einsinken gemessen und der Mittelwert gebildet.

The following results were achieved: Microemuls. from example Handle for equipment * Hydrophilicity by Equipment (s) ** Handle after 3 washes * Hydrophilicity after 3 washes (s) ** 1 1 = 2 5 1 = 2 2 2 1 = 2 10 1 = 2 4

• * The results of 5 test lobes, assessed by 4 persons, are averaged.
• ** Place 10 drops of water (50 μl) on an equipped terry cloth flap, measure the times in seconds until it sinks and form the mean value.

Overall

The Data show that the first grip of the two samples tested is equal to. The block copolymer of the invention according to Example 1, but the sought, clearly better initial hydrophilicity.

To 3 washes will turn a comparable handle and a furthermore better hydrophilicity of the invention Pattern found.

QUOTES INCLUDE IN THE DESCRIPTION

This list The documents listed by the applicant have been automated generated and is solely for better information recorded by the reader. The list is not part of the German Patent or utility model application. The DPMA takes over no liability for any errors or omissions.

Cited patent literature

• - EP 441530 [0002]
• US 5807956 [0003]
• US 5981681 [0003]
• US 6475568 [0003]
• US 5591880 [0004]
• US 5650529 [0004]
• - DE 3719086 A [0005]
• - EP 282720 A [0006]
• - US 6240929 [0007]
• - US 5098979 [0009, 0009]
• US 5153294 [0009, 0009]
• US 5166297 [0009, 0009]
• US 5602224 [0010]
• - US 6242554 [0011]
• WO 02/10257 [0012, 0012, 0051]
• WO 02/10259 [0012, 0012]
• - US 2002/0103094 A [0012, 0012]
• WO 03/78504 [0013]
• - WO 2004/090007 [0014]
• - WO 2006/103075 [0015]
• WO 2007/014930 [0016]
• - EP 2004/050472 [0058]

Claims (13)

Use of polyamine and / or polyammonium-polysiloxane copolymer compounds comprising units of the formula (I): - [QV] - (I) wherein Q is selected from the group consisting of: -NR-, -N ⁺ R ₂ - a saturated or unsaturated diaminofunctional heterocycle of the formulas:

an aromatic diaminofunctional heterocycle of the formula:

a trivalent radical of the formula:

a trivalent radical of the formula:

a tetravalent radical of the formula

wherein each R represents hydrogen or a monovalent organic radical wherein Q does not bind to a carbonyl carbon atom, V is selected from the group consisting of V ¹ , V ² and V ³ , wherein V ^{2 is} selected from divalent, straight chain, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon radicals having up to 1000 carbon atoms (the carbon atoms of the polysiloxane radical Z ^{2 as} defined below are not counted) which optionally contain one or more groups selected from -O-, -CONH-,

-CONR ² -, in which R ^{2 is} hydrogen, a monovalent, straight-chain, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon radical having up to 100 carbon atoms and having one or more groups selected from -O-, -NH-, -C ( O) - and -C (S) -, and optionally by one or more substituents selected from the group consisting of: a hydroxyl group, an optionally substituted, preferably one or more nitrogen atoms-containing heterocyclic group, amino, alkylamino , Dialkylamino, ammonium, polyether radicals, and polyetherester radicals, where, when plural groups -CONR ² are present, these may be the same or different, -C (O) - and -C (S) - may contain, and the radical V ² optionally substituted by one or more hydroxyl groups and / or by -Si (OR) _3-a (R ') _a , wherein a is an integer from 0 to 2 and R and R' are the same or different from each other and each represents an organic radical, and the radical V ^{2 is} at least one group -Z ² - of the formula

wherein R ^{1 may be the} same or different and is selected from the group consisting of: C ₁ to C ₂₂ alkyl, fluoro (C ₁ -C ₁₀ ) alkyl, C ₆ -C ₁₀ aryl and -W Si (OR) _3-a (R ') _a , wherein R, R' and a are as defined above, and W is -O- or a divalent, straight-chain, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon radical having up to 100 carbon atoms, which may contain one or more groups -C (O) -, -O-, -NH-, and -S-, and may optionally be substituted by hydroxy groups, and n ₁ = 20 to 52, V ¹ selected is selected from divalent, straight-chain, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon radicals having up to 1000 carbon atoms and optionally one or more groups selected from -O-, -CONH-,

-CONR ² -, wherein R ^{2 is} as defined above, wherein the groups R ² in the groups V ¹² and V ^{2 may be} identical or different, -C (O) -, -C (S) - and -Z ¹ - may contain, wherein -Z ¹ - a group of the formula

wherein R ^{1 is} as defined above, wherein the groups R ¹ in the groups V ¹² and V ^{2 may be the} same or different, and n ₂ = 0 to 19, and the radical V ¹² optionally substituted by one or more hydroxyl groups and or may be substituted by -Si (OR) _3-a (R ') _a , wherein a is an integer from 0 to 2 and R and R' may be the same or different and each represents an organic radical, with Provided that the radical V ^{1 has} no (poly) alkylene oxide units, and V ^{3 is} a trivalent or higher, straight-chain, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon radical having up to 1000 carbon atoms, optionally a or more groups selected from -O-, -CONH-,

-CONR ² -, wherein R ^{2 is} as defined above, -C (O) -, -C (S) -, -Z ¹ -, which is as defined above, -Z ² - which is as defined above, and Z is ³ , wherein Z ^{3 is} a tri- or higher polyorganosiloxane unit, and which may optionally be substituted by one or more hydroxyl groups and / or by -Si (OR) _3-a (R ') _a , where a is an integer is from 0 to 2 and R and R 'may be the same or different from each other and each represents an organic radical, with the proviso that - said polyamino and / or polyammonium-polysiloxane copolymer compounds at least one group -Z ¹ - , -Z ² - or Z ³ , and - that the tri- and tetravalent radicals Q serve either the branching of the main chain formed from Q and V, so that the valences which do not serve for the bond in the main chain, further from - [ QV] units carry branched branches or the tri- and tetravalent radicals Q are saturated with radicals V ³ within a l inearene backbone without formation of a branch, and and wherein the positive charge resulting from ammonium groups is neutralized by organic or inorganic acid anions, for the initial finishing of fibrous materials. Use according to claim 1, wherein V comprises repeating units of formula V ¹ and V ² . Use according to claim 1 or 2, wherein the polyamino and / or polyammonium-polysiloxane copolymer compounds have the formula (II):

wherein Q, V ¹ and V ^{2 are} as previously defined, and the ratio of w to v is about 1. Use of the polyamino and / or polyammonium-polysiloxane copolymer compounds according to one of claims 1 to 3, characterized that they have on average at least two repeating units of the formula (I). Use of the polyamino and / or polyammonium-polysiloxane copolymer compounds according to one of claims 1 to 4, characterized in that the group V ^{1 is} selected from divalent, straight-chain, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon radicals having up to 600 preferably up to 400 carbon atoms, optionally containing one or more groups selected from -O-, -CONH-, -CONR ² -, in which R ^{2 is} as defined above, -C (O) -, -C (S) - and -Z ¹ -, wherein -Z ¹ - is a group of the formula

wherein R ^{1 is} C ₁ -C ₁₈ alkyl, which may optionally be substituted by one or more fluorine atoms, or phenyl, and n _{2 is} as defined above, provided that the radical V ¹ is a Residual, which contains no (poly) alkylene oxide radical. Use of the polyamino and / or polyammonium-polysiloxane copolymer compounds according to one of Claims 1 to 5, characterized in that the group V ^{2 is} a group of the formula -V ² * -Z ² -V ² * - in which Z ^{2 is} as defined above and V ² * is a divalent straight-chain, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon radical having up to 40 carbon atoms and optionally containing one or more groups selected from -O-, -CONH- , -CONR ² -, wherein R ^{2 is} as defined above, -C (O) - and -C (S) - may contain, and the radical V ² * may optionally be substituted by one or more hydroxyl groups. Use of the polyamino and / or polyammonium-polysiloxane copolymer compounds according to one of claims 1 to 6, characterized in that V ^{1 is} selected from divalent, straight-chain, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon radicals having up to 100 carbon atoms which may optionally contain one or more groups selected from -Z ¹ , wherein -Z ¹ - is a group of the formula

is wherein R ^{1 is} as defined above, wherein the groups R ¹ in the groups V ¹ and V ^{2 may be the} same or different, and n ₂ = 0 to 19, and the radical V ¹ optionally substituted by one or more hydroxyl groups and or may be substituted by -Si (OR) _3-a (R ') _a wherein a is an integer from 0 to 2 and R and R' may be the same or different and each represents an organic radical. Use of the polyamino and / or polyammonium-polysiloxane copolymer compounds according to one of Claims 1 to 7, characterized in that the group V ^{1 is} a radical -R ⁹ - in which R ^{9 is} a divalent, saturated or mono- or polyunsaturated one , straight-chain or branched hydrocarbon radical having from 2 to 25 carbon atoms. Use of compositions containing at least a polyamino and / or polyammonium-polysiloxane copolymer compounds such as in any of claims 1 to 8, in combination with at least one other polydiorganosiloxane compound different therefrom. Use of the polyamine and / or polyammonium-polysiloxane copolymer compounds according to any one of claims 1 to 8 and the composition according to claim 9, wherein the fiber materials are selected are made of natural and synthetic fibrous materials, including cellulose, wool, cotton, silk and synthetic fibers. Process for the initial finishing of fiber materials, which involves the treatment of the fiber materials with at least one Polyamino and / or polyammonium-polysiloxane copolymer compound, as defined in any one of claims 1 to 8 or one A composition as defined in claim 9, or an aqueous emulsion including thereof. Aqueous emulsion containing at least a polyamino and / or polyammonium-polysiloxane copolymer compounds, as defined in any one of claims 1 to 8 or one Composition as defined in claim 9, and optionally one or more surfactants and optionally one or more nitrogen-free Polysiloxane. Use of the aqueous emulsion according to Claim 12 for the original equipment of fiber materials.